N-phenylsulfonyl-N&#39;-pyrimidinylureas

ABSTRACT

N-phenylsulfonyl-N&#39;-pyrimidinyl- and -triazinylureas of the general formula ##STR1## and the salts of these compounds with amines, alkali metal or alkaline-earth metal bases or with quaternary ammonium bases have good selective, pre- and post-emergence, herbicidal and growth-regulating properties. 
     The symbols in this formula have the following meanings: 
     A is a C 3  -C 6  -alkynyl group, a C 1  -C 6  -alkyl group which is substituted by halogen, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylthio, C 1  -C 4  -alkylsulfinyl, C 1  -C 4  -alkylsulfonyl, C 1  -C 4  -haloalkoxy, C 1  -C 4  -haloalkylthio, C 1  -C 4  -haloalkylsulfinyl or C 1  -C 4  -haloalkylsulfonyl, or it is a C 2  -C 6  -alkenyl group substituted by one of the above substituents, 
     E is the methine group or nitrogen, 
     X is oxygen, sulfur, or a sulfinyl or sulfonyl bridge, 
     Z is oxygen or sulfur, 
     m is the number one or two, 
     R 1  is hydrogen, halogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl, or a --Y--R 6  group, 
     R 2  is hydrogen, halogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 1  -C 4  -haloalkyl, or a group --Y--R 6 , --COOR 7 , --NO 2  or --CO--NR 8  --R 9 , 
     R 3  is hydrogen, C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylthio, C 1  -C 4  -haloalkyl, C 1  -C 4  -haloalkoxy, halogen or alkoxyalkyl having at most 4 carbon atoms, 
     R 4  is hydrogen, methyl or ethyl, 
     R 5  is hydrogen, C 1  -C 4  -alkyl, C 1  -C 3  -alkoxy, methoxymethyl, cyanomethyl or cyanoethyl, 
     R 6  and R 7  are each C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 2  -C 6  -alkynyl, 
     R 8  and R 9  independently of one another are each hydrogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 2  -C 6  -alkynyl, and 
     Y is oxygen, sulfur, or a sulfinyl or sulfonyl bridge, and A can also be C 2  -C 6  -alkenyl when X is oxygen.

This is a divisional of application Ser. No. 430,635 filed on Sept. 30,1982, now U.S. Pat. No. 4,579,584, issued Apr. 1, 1986.

The present invention relates to novel N-phenylsulfonyl-N'-pyrimidinyl-and -triazinylureas which have a herbicidal action and an actionregulating plant growth, to processes for producing them, tocompositions containing them as active ingredients, and also to the usethereof for combating weeds, particularly selectively in cultivatedcrops, or for regulating and reducing plant growth.

The N-phenylsulfonyl-N'-pyrimidinyl- and -triazinylureas according tothe invention correspond to the general formula I ##STR2## wherein A isa C₃ -C₆ -alkynyl group, a C₁ -C₆ -alkyl group which is substituted byhalogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulfinyl, C₁-C₄ -alkylsulfonyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -haloalkylthio, C₁ -C₄-haloalkylsulfinyl or C₁ -C₄ -haloalkylsulfonyl, or it is a C₂ -C₆-alkenyl group substituted by one of the above substituents,

E is the methine group or nitrogen,

X is oxygen, sulfur, or a sulfinyl or sulfonyl bridge,

Z is oxygen or sulfur,

m is the number one or two,

R₁ is hydrogen, halogen, C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl, or a --Y--R₆group,

R₂ is hydrogen, halogen, C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or C₁ -C₄-haloalkyl, or a group --Y--R₆, --COOR₇, --NO₂ or --CO--NR₈ --R₉,

R₃ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, halogen or alkoxyalkyl having at most 4carbon atoms,

R₄ is hydrogen, methyl or ethyl,

R₅ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₃ -alkoxy, methoxymethyl,cyanomethyl or cyanoethyl,

R₆ and R₇ are each C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or C₂ -C₆ -alkynyl,

R₈ and R₉ independently of one another are each hydrogen, C₁ -C₅ -alkyl,C₂ -C₅ -alkenyl or C₂ -C₆ -alkynyl, and

Y is oxygen, sulfur, or a sulfinyl or sulfonyl bridge, and A can also beC₂ -C₆ -alkenyl when X is oxygen; and the invention relates also to thesalts of these compounds.

Urea compounds, triazine compounds and pyrimidine compounds havingherbicidal activity are known in general. There have recently beendescribed arylsulfamoyl-heterocyclyl-aminocarbamoyl compounds having aherbicidal action and an action regulating plant growth, for example inthe European Patent Publications Nos. 9419 and 10560, or in the DutchPatent Specification No. 121788.

Alkyl in the definitions is straight-chain or branched-chain alkyl, forexample: methyl, ethyl, n-propyl, i-propyl, the four isomeric butylgroups, n-amyl, i-amyl, 2-amyl, 3-amyl, n-hexyl or i-hexyl.

By alkoxy is meant: methoxy, ethoxy, n-propyloxy, i-propyloxy and thefour isomeric butyloxy groups in particular however methoxy, ethoxy ori-propoxy.

Examples of alkylthio are: methylthio, ethylthio, n-propylthio,i-propylthio and n-butylthio, but especially methylthio and ethylthio.

Examples of alkenyl groups are: vinyl, allyl, isopropenyl, 1-propenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-isobutenyl, 2-isobutenyl, 1-pentenyl,2-pentenyl, 3-pentenyl and 4-pentenyl, especially however vinyl, allyland 4-pentenyl.

Examples of alkylsulfinyl are: methylsulfinyl, ethylsulfinyl,n-propylsulfinyl and n-butylsulfinyl, in particular methylsulfinyl andethylsulfinyl.

Examples of alkylsulfonyl are: methylsulfonyl, ethylsulfonyl,n-propylsulfonyl and n-butylsulfonyl, especially however methylsulfonyland ethylsulfonyl.

Halogen in the definitions, as well as being in haloalkyl, -alkoxy,-alkylsulfinyl, -alkylsulfonyl and -alkylthio, is fluorine, chlorine andbromine, preferably fluorine and chlorine.

By haloalkyl or by haloalkyl moieties of the abovedefined substituentsare accordingly meant for example: chloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl,1,1,2,2-tetrafluoroethyl, pentafluoroethyl,1,1,2-trifluoro-2-chloroethyl, 2,2,2-trifluoro-1,1-dichloroethyl,pentachloroethyl, 3,3,3-trifluoropropyl, 2,2-dichloropropyl or1,1,2,3,3,3-hexafluoropropyl, particularly however: fluoromethyl,chloromethyl, difluoromethyl and trifluoromethyl.

Alkynyl groups in the definitions of the above symbols are as a rule:propargyl, 2-butynyl and 3-butynyl, as well as isomeric pentynyl orhexynyl groups; the alkynyl group is preferably however propargyl or 2-or 3-butynyl.

The invention embraces also the salts which the compounds of the formulaI can form with amines, alkali metal bases and alkaline-earth metalbases or quaternary ammonium bases. To be emphasised among the alkalimetal and alkaline-earth metal hydroxides as salt formers are thehydroxides of lithium, sodium, potassium, magnesium or calcium,especially however those of sodium or potassium. Examples of aminessuitable for forming salts are: primary, secondary and tertiaryaliphatic and aromatic amines, such as methylamine, ethylamine,propylamine, i-propylamine, the four isomeric butylamines,dimethylamine, diethylamine, diethanolamine, dipropylamine,diisopropylamine, di-n-butylamine, pyrolidine, piperidine, morpholine,trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine,quinoline and i-quinoline, in particular however ethyl-, propyl,diethyl- or triethylamine, but especially isopropylamine anddiethanolamine. Examples of quaternary ammonium bases are in general thecations of haloammonium salts, for example the tetramethylammoniumcation, the trimethylbenzylammonium cation, the triethylbenzylammoniumcation, the tetraethylammonium cation or the trimethylethylammoniumcation, but also the ammonium cation.

Preferred compounds of the formula I are those in which

(a) X and

(b) Z are oxygen, and

(c) m is the number one,

(d) R₄ and R₅ together contain no more than 4 carbon atoms, and

(e) a group --X--A in the phenyl ring is in the 2-position with respectto the sulfonamide group.

By combination of the preferred features, there is formed a furtherpreferred group of compounds of the formula I in which X and Y areoxygen, m is the number one, R₄ and R₅ together contain no more than 4carbon atoms, and the --X--A group in the phenyl ring occupies the2-position with respect to the sulfonamide group.

This preferred subgroup in its turn breaks down into the following twolikewise further preferred groups containing compounds wherein

(α) A is a C₁ -C₄ -haloalkyl group, or

(β) A is C₃ -C₄ -alkynyl, C₂ -C₆ -alkenyl or C₂ -C₆ -haloalkenyl or C₁-C₃ -alkyl substituted by C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulfinyl or C₁ -C₄ -alkylsulfonyl.

A further preference within the groups α and β is where in each case R₁is hydrogen, and R₂ is hydrogen, halogen, methyl or --COO--C₁ -C₃-alkyl.

Compounds among these to be emphasised are those in which R₁ and R₂ arehydrogen.

More especially preferred of these compounds are those wherein R₃ ismethoxy, ethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methyl, ethyl,fluoromethyl or chloromethyl, R₄ is hydrogen, methyl or ethyl, and R₅ ismethyl or ethyl.

The following are mentioned as preferred individual compounds:

N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-dimethylamino-6-methoxy-1,3,5-triazin-2-yl)-urea,

N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-dimethylamino-6-methoxypyrimidin-2-yl)-urea,and

N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-methylamino-6-methoxypyrimidin-2-yl)-urea.

The compounds of the formula I are produced in an inert organic solvent.

One process for obtaining the compounds of the formula I comprisesreacting a phenylsulfonamide of the formula II ##STR3## wherein A, R₁,R₂, X and m have the meanings defined under the formula I, in thepresence of a base, with an N-pyrimidinyl- or -triazinylcarbamate of theformula III ##STR4## wherein E, R₃, R₄, R₅ and Z have the meaningsdefined under the formula I.

Compounds of the formula I are produced, using a second process, byreacting a phenylsulfonylisocyanate or -isothiocyanate of the formula IV##STR5## wherein A, R₁, R₂, m, X and Z have the meanings defined underthe formula I, in the presence or absence of a base, with an amine ofthe formula V ##STR6## wherein E, R₃, R₄ and R₅ have the meaningsdefined under the formula I.

A further process for producing compounds of the formula I comprisesreacting a sulfonamide of the above formula II, in the presence orabsence of a base, with an isocyanate or isothiocyanate of the formulaVI ##STR7## wherein E, R₃, R₄, R₅ and Z have the meanings defined underthe formula I.

Furthermore, the compounds of the formula I can be obtained by reactingan N-phenylsulfonylcarbamate of the formula VII ##STR8## wherein A, R₁,R₂, m and X have the meanings defined under the formula I, with an amineof the formula V given above.

Finally, the compounds of the formula I are produced also by reacting asulfonylurea of the formula VIII ##STR9## wherein A, E, R₁, R₂, R₃, X, Zand m have the meanings defined under the formula I, and Hal is chlorineor bromine, with an amine of the formula IX ##STR10## wherein R₄ and R₅have the meanings defined under the formula I.

The resulting ureas of the formula I can if desired be converted, bymeans of amines, alkali metal or alkaline-earth metal hydroxides orquaternary ammonium bases, into addition salts. This is effected forexample by reaction with the equimolar amount of a base, and removal ofthe solvent by evaporation.

The starting materials of the formulae II, IV, VII, VIII andortho-substituted hydroxyphenyl- or substitutedortho-hydroxyphenylsulfonamides of the formula X ##STR11## wherein R₁and R₂ have the meanings defined under the formula I, and X' is oxygenor sulfur, are known, as starting products of specific sulfonamiderepresentatives of the formula II, from the European Patent ApplicationNo. 44 807.

Some of the starting materials of the formulae III and VI are known, andnew compounds of the formulae III and VI can be obtained by knownmethods from corresponding compounds of the formula V.

Novel fluoroalkoxy-aminopyrimidines and -triazines of the formula V andtheir production, as well as the production of corresponding compoundsof the formulae III and VI therefrom, are described in U.S. Pat. No.4,579,584, the disclosure of which is incorporated herein by reference.Other amines of the formula V are known and in part obtainablecommercially; or they can be produced by known methods (cp. "TheChemistry of Heterocyclic Compounds", Vol. XIV, Interscience Publishers,New York, London).

Isocyanates of the formula VI can be produced by reaction of amines ofthe formula V with oxalyl chloride in chlorinated hydrocarbons assolvent.

The starting materials of the formula IX are known, or can be producedby known methods.

The reactions to compounds of the formula I are advantageously performedin aprotic, inert, organic solvents, such as methylene chloride,tetrahydrofuran, acetonitrile, dioxane and toluene.

The reaction temperatures are preferably between -20° and +120° C. Thereactions proceed in general slightly exothermically, and can be carriedout at room temperature. For the purpose of shortening the reaction timeor for initiating the reaction, it is advantageous to apply heat for ashort time up to the boiling point of the reaction mixture. The reactiontimes can also be shortened by the addition of some drops of a base orof isocyanate as a reaction catalyst.

The final products can be isolated by concentration by evaporationand/or by removal of the solvent by evaporation, and purified byrecrystallization or trituration of the solid residue in solvents inwhich they do not readily dissolve, such as ether, aromatic hydrocarbonsor chlorinated hydrocarbons.

The active substances of the formula I are stable compounds, and thehandling of them necessitates no special precautions being taken.

In smaller applied amounts, the compounds of the formula I arecharacterised by good selective growth-inhibiting and selectiveherbicidal properties, which render them excellently suitable for use incrops of useful plants, especially in crops of sugar cone cereals,cotton, soya-bean, maize and rice. Also destroyed in some cases areweeds which hitherto could be dealt with only be the use of totalherbicides.

The mode of action of these active substances is unusual. Many arecapable of being translocated, that is to say, they are taken up by theplant and transported to other locations, where they produce the desiredeffect. It is thus possible for example by surface treatment ofperennial weeds to destroy them at their roots. The novel compounds ofthe formula I are effective in applied amounts which are very smallcompared with the amounts required to obtain the same effect using otherherbicides and plant-growth regulators.

The compounds of the formula I also have excellent properties forregulating plant growth, the effects of which can be an increase in theyield of cultivated plants or of harvested crops. Many compounds of theformula I also exhibit an action reducing plant growth to an extentdependent on the concentration. Both monocotyledons and dicotyledons areimpaired in their growth.

Thus, for example, the leguminosae frequently planted as cover crops inagriculture in tropical regions can be selectively inhibited in theirgrowth by the compounds of the formula I, the result being that soilerosion between the cultivated plants is prevented, without the covercrops being able to complete with the main cultivated crop.

A reduction of the vegetative growth enables in the case of manycultivated plants the crop density to be increased, so that higheryields for the same area of land can be achieved.

An additional factor contributing to the increase in yield with the useof growth inhibitors is that the formation of blossom and fruit benefitsto a greater extent from the nutritive substances, because thevegetative growth is restricted.

In the case of monocotyledonous plants, for example grasses, orcultivated plants such as cereals, a reduction of vegetative growth issometimes desirable and advantageous. A reduction of growth of this kindis of economical interest with regard to, among other things, grasses,for as a consequence it is possible to reduce the frequency of thecutting of grass in ornamental gardens, parks and sports grounds, oralong the verges of highways. Of importance also is the inhibition ofthe growth of herbaceous and ligneous plants at the edges of roads andin the vicinity of overhead transmission lines, or quite generally inareas where a strong growth is undesirable.

Also important is the application of growth regulators for reducing thegrowth in height of cereals, since a shortening of the stems lessens orcompletely removed the danger of the snapping off (flattening) of theplants before harvesting. Furthermore, growth regulators can result in astrengthening of the stems of cereal crops, a further factor acting toprevent bending of the stems of the plants.

The compounds of the formula I are likewise suitable for preventing thesprouting of stored potatoes. Shoots frequently form on potatoes beingstored during the winter, and these shoots cause shrinkage, loss inweight and rotting.

With larger applied amounts of active substance, all the tested plantsare impaired in their development to the extent that they wither.

The present invention relates also to herbicidal andplant-growth-regulating compositions containing a novel activeingredient of the formula I, and also to processes for the pre- andpost-emergence combating of weeds, and for the reduction of growth ofmonocotyledonous and dicotyledonous plants, particularly that ofgrasses, tropical cover crops and side shoots of tobacco plants.

The compounds of the formula I are used either in an unmodified form orpreferably in compositions, together with auxiliaries customarilyemployed in formulation practice, and are thus processed, in a knownmanner, for example into the form of emulsion concentrates, directlysprayable or dilutable solutions, diluted emulsions, wettable powders,soluble powders, dusts or granulates, and also encapsulations in forexample polymeric substances. The application processes, such asspraying, atomising, dusting, scattering or pouring, and likewise thetype of composition, are selected to suit the objects to be achieved andthe given conditions.

The formulations, that is to say, the compositions or preparationscontaining the active ingredient of the formula I and optionally a solidor liquid additive, are produced in a known manner, for example by theintimate mixing and/or grinding of the active ingredients withextenders, such as with solvents, solid carriers and optionallysurface-active compounds (tensides).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionsC₈ to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalicesters, such as dibutyl- or dioctylphthalate, aliphatic hydrocarbons,such as cyclohexane or paraffins, alcohols and glycols, as well asethers and esters thereof, such as ethanol, ethylene glycol, ethyleneglycol monomethyl or -ethyl ethers, ketones, such as cyclohexanone,strongly polar solvents, such as N-methyl-2-pyrrolidone,dimethylsulfoxide or dimethylformamide, as well as optionally epoxidisedvegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders,are as a rule natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties, it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, ground brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. There can also be used a great number of pre-granulatedmaterials of inorganic or organic nature, such as in particular dolomiteor ground plant residues.

Suitable surface-active compounds are, depending on the nature of theactive substance of the formula I to be formulated, nonionic, cationicand/or anionic tensides having good emulsifying, dispersing and wettingproperties. By `tensides` are also meant mixtures of tensides.

Suitable anionic tensides are both so-called water-soluble soaps as wellas water-soluble, synthetic, surface-active compounds.

Soaps which are applicable are the alkali metal, alkaline-earth metal oroptionally substituted ammonium salts of higher fatty acids (C₁₀ -C₂₂),for example the Na or K salts of oleic or stearic acid, or of naturalfatty acid mixtures, which can be obtained for example from coconut oilor tallow oil. Also to be mentioned are the fatty acid-methyl-taurinesalts.

So-called synthetic tensides are however more frequently used,particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates. The fatty sulfonates or sulfates areas a rule in the form of alkali metal, alkaline-earth metal oroptionally substituted ammonium salts, and contain an alkyl group having8 to 22 C atoms, `alkyl` including also the alkyl moiety of acyl groups,for example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuricacid ester or of a fatty alcohol sulfate mixture produced from naturalfatty acids. Included among these are also the salts of sulfuric acidesters and sulfonic acids of fatty alcohol ethylene oxide adducts. Thesulfonated benzimidazole derivatives preferably contain 2 sulfonic acidgroups and a fatty acid group having 8-22 C atoms. Alkylarylsulfonatesare for example the Na, Ca or triethanolamine salts ofdodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid-formaldehyde condensation product. Alsosuitable are corresponding phosphates, for example salts of thephosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct.

Suitable nonionic tensides are in particular polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, saturated orunsaturated fatty acids and alkylphenols, which can contain 3 to 30glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of thealkylphenols.

Further suitable nonionic tensides are the water-soluble polyethyleneoxide adducts, which contain 20 to 250 ethylene glycol ether groups and10 to 100 propylene glycol ether groups, with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usuallycontain 1 to 5 ethylene glycol units per propylene glycol unit. Examplesof nonionic tensides which may be mentioned are:nonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethyleneoxy adducts, tributylphenoxypolyethoxyethanol,polyethylene glycol and octylphenoxypolyethoxyethanol. Suitable also arefatty acid esters of polyoxyethylenesorbitan, such aspolyoxyethylenesorbitan-trioleate.

In the case of the cationic tensides, they are in particular quaternaryammonium salts which contain as N-substituents at least one alkyl grouphaving 8 to 22 C atoms and, as further substituents, lower, optionallyhalogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts arepreferably in the form of halides, methyl sulfates or ethyl sulfates,for example stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The tensides customarily used in formulation practice are described,inter alia, in the following publications: "Mc Cutcheon's Detergents andEmuslifiers Annual" MC Publishing Corp., Ridgewood, N.J., 1979; andSisley and Wood, "Encyclopedia of Surface Active Agents", ChemicalPublishing Co., Inc. New York, 1964.

The agrochemical preparations contain as a rule 0.1 to 95%, especially0.1 to 80%, of active ingredient of the formula I, 1 to 99.9% of a solidor liquid additive, and 0 to 25%, particularly 0.1 to 25%, of a tenside.

Preferred formulations are made up in particular as follows (%=percentby weight):

Emusifiable concentrates

active ingredient: 1 to 20%, preferably 5 to 10%

surface active agent: 5 to 30%, preferably 10 to 20%

liquid carrier: 50 to 94%, preferably 70 to 85%.

Dusts

active ingredient: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90% preferably 99.9 to 99%.

Suspension concentrates

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 25%, preferably 90 to 30%

surface-active agent: 1 to 40%, preferably 2 to 30%.

Wettable powders

active ingredient: 0.5 to 90%, preferably 1 to 80%

surface-active agent: 0.5 to 20%, preferably 1 to 15%

solid-carrier: 5 to 95%, preferably 15 to 90%.

Granulates

active ingredient: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%.

Whereas commerical products are preferably in the form of concentratedcompositions, the compositions employed by the end-user are as a rulediluted. The preparations can for application be diluted down to 0.001%of active ingredient. The applied amounts are usually 0.001 to 10 kg,preferably 0.025 to 5 kg, of active substance per hectare.

The compositions can also contain additive such as stabilisers,antifoaming agents, viscosity regulators, binders and adhesives, as wellas fertilisers or other active substances for obtaining special effects.

In the following Examples, the temperatures are given in degreesCentigrade (°C.), and pressures in millibars (mb).

PRODUCTION EXAMPLES EXAMPLE 1N-(2-Difluromethoxyphenyl-sulfonyl)-N'-(4-dimethylamino-6-methoxy-1,3,5-triazin-2-yl)-urea

(a) To the suspension of 80.3 g of2-amino-4-chloro-6-methoxy-1,3,5-triazine in 400 ml of absolute dioxaneare added dropwise, within 10 minutes, 124.6 g of2-difluoromethoxy-sulfonylisocyanate in 100 ml of dioxane. The reactionmixture is heated for 3 hours at 90°-100° C. After cooling andconcentrating the reaction solution by evaporation, the yield is 180 gofN-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-chloro-6-methoxy-1,3,5-triazin-2-yl)-urea,m.p. 167°-168° C.

(b) 3.0 g of dimethylamine are introduced at 20°-30° C., with cooling,into a solution of 8.2 g ofN-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-chloro-6-methoxy-1,3,5-triazin-2-yl)-ureain 80 ml of dioxane. After the formed suspension has been stirred for afurther 30 minutes, it is taken up in 500 ml of 0.1N hydrochloric acid,and the product which has precipitated is separated by filtration;yield: 7.7 g ofN-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-dimethylamino-6-methoxy-1,3,5-triazin-2-yl)-urea,m.p. 171°-172° C.

EXAMPLE 2N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-(4-tert-butylamino-6-methoxy-1,3,5-triazin-2-yl)-urea

A mixture of 5.0 g of 2-difluoromethoxyphenyl-sulfonylisocyanate and 4.0g of 2-amino-4-tert-butylamino-6-methoxy-1,3,5-triazine is stirred in 60ml of absolute dioxane for 3 hours at 70°-80° C. After filtration of thehot reaction mixture through active charcoal, 6.9 g ofN-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-tert-butylamino-6-methoxy-1,3,5-triazin-2-yl)-urea,m.p. 213°-214° C., crystallise out on cooling of the solution.

The final products listed in the subsequent Tables are obtained in ananalogous manner.

                                      TABLE 1                                     __________________________________________________________________________     ##STR12##                                                                    No.                                                                              A             X E  R.sub.3  R.sub.4                                                                           R.sub.5   m.p. °C.                  __________________________________________________________________________    1  CHF.sub.2     O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  202-203                          2  CHF.sub.2     O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  3  CHF.sub.2     O CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   4  CHF.sub.2     O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         5  CHF.sub.2     O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 6  CHF.sub.2     O CH OCH.sub.3                                                                              CH.sub.3                                                                          H         170-171                          7  CHF.sub.2     O CH OCH.sub.3                                                                              H   H                                          8  CHF.sub.2     O CH Cl       CH.sub.3                                                                          CH.sub.3  218-219                          9  CHF.sub.2     O CH CH.sub.3 CH.sub.3                                                                          CH.sub.3                                   10 CHF.sub.2     O CH CH.sub.3 CH.sub.3                                                                          OCH.sub.3                                  11 CHF.sub.2     O CH OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   12 CHF.sub.2     O CH OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  13 CHF.sub.2     O CH OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3  193-194                          14 CHF.sub.2     O CH OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  15 CHF.sub.2     O CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   H                                          16 CHF.sub.2     O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 17 CHF.sub.2     O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                                                                      172-173                          18 CHF.sub.2     O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   19 CHF.sub.2     O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  20 CHF.sub.2     O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3  172-173                          21 CHF.sub.2     O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  22 CHF.sub.2     O N  CH.sub.3 CH.sub.3                                                                          CH.sub.3  193-194                          23 CHF.sub.2     O CH CH.sub.2 Cl                                                                            CH.sub.3                                                                          CH.sub.3  170-171                          24 CHF.sub.2     S CH OCH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                 CH.sub.3                                   25 CHF.sub.2     S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   26 CHF.sub.2     S CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   27 CHF.sub.2     S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         28 CHF.sub.2     S CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          29 CHF.sub.2     S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 30 CHF.sub.2     S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  200-201                          31 CHF.sub.2     O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  32 CHF.sub.2     O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   33 CHF.sub.2     S N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  34 CHF.sub.2     S N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   OCH.sub.3                                  35 CHF.sub.2     S N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  36 CHF.sub.2     S N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         37 CHF.sub.2     S N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 38 CHF.sub.2     S N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   39 CHF.sub.2     S N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3                                   40 CHF.sub.2     S N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  41 CHF.sub.2     S N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  42 CHF.sub.2     S CH Cl       CH.sub.3                                                                          CH.sub.3                                   43 CHF.sub.2     S CH CH.sub.3 CH.sub.3                                                                          CH.sub.3                                   44 CHF.sub.2     S CH CH.sub.3 CH.sub.3                                                                          OCH.sub.3                                  45 CHF.sub.2     S CH OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   46 CHF.sub.2     S CH OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  47 CHF.sub.2     S CH OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3                                   48 CHF.sub.2     S CH OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  49 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                 CH.sub.3                                   50 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  51 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   52 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         53 (CH.sub. 2).sub.2OCH.sub.3                                                                  O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          54 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 55 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  202-203                          56 (CH.sub.2).sub.2OCH.sub.3                                                                   S CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  57 (CH.sub.2).sub.2OCH.sub.3                                                                   S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   58 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  59 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   OCH.sub.3                                  60 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   61 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         62 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 63 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   64 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub. 2CF.sub.3                                                                     CH.sub.3                                                                          CH.sub.3                                   65 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  66 (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  67 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH Cl       CH.sub.3                                                                          CH.sub.3                                   68 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH CH.sub.3 CH.sub.3                                                                          CH.sub.3                                   69 (CH.sub.2).sub.2OCH.sub.3                                                                   O CH CH.sub.3 CH.sub.3                                                                          OCH.sub.3                                  70 CH.sub.2CH.sub.2 Cl                                                                         O CH OCH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                 CH.sub.3                                   71 CH.sub.2CH.sub.2 Cl                                                                         O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  72 CH.sub.2CH.sub.2 Cl                                                                         O CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   73 CH.sub.2CH.sub.2 Cl                                                                         O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         74 CH.sub.2CH.sub.2 Cl                                                                         O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          75 CH.sub.2CH.sub.2 Cl                                                                         O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 76 CH.sub.2CH.sub.2 Cl                                                                         O CH OCH.sub. 3                                                                             CH.sub.3                                                                          CH.sub.3                                   77 CH.sub.2CH.sub.2 Cl                                                                         S CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  78 CH.sub.2CH.sub.2 Cl                                                                         S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   79 CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  80 CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   OCH.sub.3                                  81 CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   82 CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         83 CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 84 CH.sub.2CH.sub.2 Cl                                                                         O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   85 CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3                                   86 CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  87 CH.sub.2CH.sub.2 Cl                                                                         O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  88 CH.sub.2CH.sub.2 Cl                                                                         O CH Cl       CH.sub.3                                                                          CH.sub.3                                   89 CH.sub.2CH.sub.2 Cl                                                                         O CH CH.sub.3 CH.sub.3                                                                          CH.sub.3                                   90 CH.sub.2CH.sub.2 Cl                                                                         O CH CH.sub.3 CH.sub.3                                                                          OCH.sub.3                                  91 CH.sub.2CCH   O CH OCH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                 CH.sub.3                                   92 CH.sub.2CCH   O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  93 CH.sub.2CCH   O CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   94 CH.sub.2CCH   O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         95 CH.sub.2CCH   O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          96 CH.sub.2CCH   O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 97 CH.sub.2CCH   O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   98 CH.sub.2CCH   S CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  99 CH.sub.2CCH   S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   100                                                                              CH.sub.2CCH   O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  101                                                                              CH.sub.2CCH   O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   OCH.sub.3                                  102                                                                              CH.sub.2CCH   O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   103                                                                              CH.sub.2CCH   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         104                                                                              CH.sub.2CCH   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 105                                                                              CH.sub.2CCH   O N  OC.sub.2 H.sub.5                                                                       CH.sub. 3                                                                         CH.sub.3                                   106                                                                              CH.sub.2CCH   O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3  160-164                          107                                                                              CH.sub.2CCH   O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  108                                                                              CH.sub.2CCH   O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  109                                                                              CH.sub.2CCH   O CH Cl       CH.sub.3                                                                          CH.sub.3                                   110                                                                              CH.sub.2CCH   O CH CH.sub.3 CH.sub.3                                                                          CH.sub.3                                   111                                                                              CH.sub.2CCH   O CH CH.sub.3 CH.sub.3                                                                          OCH.sub.3                                  112                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                 CH.sub.3                                   113                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  114                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   115                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         116                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          117                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 118                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   119                                                                              CH.sub.2CHCH.sub.2                                                                          S CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  120                                                                              CH.sub.2CHCH.sub.2                                                                          S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   121                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  122                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   OCH.sub.3                                  123                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   124                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         125                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 126                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   127                                                                              CH.sub.2 CHCH.sub.2                                                                         O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3                                   128                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  129                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  130                                                                              CH.sub.2CHCH.sub.2                                                                          O CH Cl       CH.sub.3                                                                          CH.sub.3                                   131                                                                              CH.sub.2CHCH.sub.2                                                                          O CH CH.sub.3 CH.sub.3                                                                          CH.sub.3                                   132                                                                              CH.sub.2CHCH.sub.2                                                                          O CH CH.sub.3 CH.sub.3                                                                          OCH.sub.3                                  133                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                 CH.sub.3                                   134                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  135                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   136                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         137                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          138                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 139                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   140                                                                              CF.sub.2CHF.sub.2                                                                           S CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  141                                                                              CF.sub.2CHF.sub.2                                                                           S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   142                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  143                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   OCH.sub.3                                  144                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                   CH.sub.3                                   145                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CH.sub.2CN                         146                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2CN                                 147                                                                              CF.sub.2CHF.sub.2                                                                           O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          CH.sub.3                                   148                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3                                   149                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          OCH.sub.3                                  150                                                                              CF.sub.2CHF.sub.2                                                                           O N  OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                          OCH.sub.3                                  151                                                                              CF.sub.2CHF.sub.2                                                                           O CH Cl       CH.sub.3                                                                          CH.sub.3                                   152                                                                              CF.sub.2CHF.sub.2                                                                           O CH CH.sub.3 CH.sub.3                                                                          CH.sub. 3                                  153                                                                              CF.sub.2CHF.sub.2                                                                           O CH CH.sub.3 CH.sub.3                                                                          OCH.sub.3                                  154                                                                              CF.sub.3      O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   155                                                                              CF.sub.3      O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  156                                                                              CF.sub.3      O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  157                                                                              CF.sub.3      O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  181-182                          158                                                                              C.sub.2 F.sub.5                                                                             O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  189-190                          159                                                                              C.sub.2 F.sub.5                                                                             O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  160                                                                              C.sub.2 F.sub.5                                                                             O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  175-176                          161                                                                              C.sub.2 F.sub.5                                                                             O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  162                                                                              CF.sub.2CHFCl O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  163-166                          163                                                                              CF.sub.2CHFCl O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   164                                                                              CF.sub.2CHFCl O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  165                                                                              CF.sub.2CHFCl O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  166                                                                              CH.sub.2OCH.sub.3                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   167                                                                              CH.sub.2OCH.sub.3                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  168                                                                              CH.sub.2OCH.sub.3                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   169                                                                              CH.sub.2OCH.sub.3                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  170                                                                              CH.sub.2C(CH.sub.3)CH.sub.2                                                                 O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  171                                                                              CH.sub.2C(CH.sub.3)CH.sub.2                                                                 O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   172                                                                              CH.sub.2C(CH.sub.3)CH.sub.2                                                                 O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  153-154                          173                                                                              CH.sub.2C(CH.sub.3)CH.sub.2                                                                 O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  174                                                                              CClCHCl       O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  233-234                          175                                                                              CClCHCl       O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  176                                                                              CClCHCl       O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  206-207                          177                                                                              CClCHCl       O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  178                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  171-172                          179                                                                              CHF.sub.2     O N  SCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  184-185                          180                                                                              CF.sub.2CHFCl O CH CH.sub.3 CH.sub.3                                                                          CH.sub.3                                   181                                                                              CHF.sub.2     S N  SCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   182                                                                              CHF.sub.2     O N  i-C.sub.3 H.sub.7                                                                      CH.sub.3                                                                          CH.sub.3  150-153                          183                                                                              CHF.sub.2     S N  i-OC.sub.3 H.sub.7                                                                     CH.sub.3                                                                          CH.sub.3  178-180                          184                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              H   H         >250                             185                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              H   t-C.sub.4 H.sub.9                                                                       213-214                          186                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              H   C.sub.2 H.sub.5                                                                         191-192                          187                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              H   CH.sub.3  188-190                          188                                                                              CHF.sub.2     S N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  188-190                          189                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3 122 (decomp.)                    190                                                                              CHF.sub.2     O N  Cl       CH.sub.3                                                                          CH.sub.3  199-200                          191                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  173-174                          192                                                                              CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  181-182                          193                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  169-170                          194                                                                              CH.sub.2CCH   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  197-199                          195                                                                              CH.sub.2CHCH CH.sub.3                                                                       O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  182-184                          196                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  177-180                          197                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              CH.sub.3                                                                          C.sub.2 H.sub.5                                                                         172-173                          198                                                                              (CH.sub.2).sub.2OC.sub.2 H.sub.5                                                            O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   199                                                                              (CH.sub.2).sub.2OC.sub.2 H.sub.5                                                            O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  200                                                                              (CH.sub.2).sub.2OC.sub.2 H.sub.5                                                            O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   201                                                                              (CH.sub.2).sub.2OC.sub.2 H.sub.5                                                            O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  202                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   203                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  204                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   O CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   205                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   O CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  206                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          207                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   S N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   208                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   S N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          209                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   S N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   210                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   S N  OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  211                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   S CH OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                   212                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   S CH OCH.sub.3                                                                              CH.sub.3                                                                          OCH.sub.3                                  213                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   S CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          214                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   S N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          215                                                                              CClCHCl       O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          216                                                                              CClCHCl       O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          217                                                                              CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          218                                                                              CH.sub.2CCH   O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          219                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          220                                                                              CF.sub.2 CHF.sub.2                                                                          O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          221                                                                              CF.sub.3      O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          222                                                                              CF.sub.3      O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          223                                                                              C.sub.2 F.sub.5                                                                             O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          224                                                                              C.sub.2 F.sub.5                                                                             O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          225                                                                              CF.sub.2CHFCl O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          226                                                                              CF.sub.2CHFCl O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          227                                                                              CH.sub.2OCH.sub.3                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          H                                          228                                                                              CH.sub.2OCH.sub.3                                                                           O CH OCH.sub.3                                                                              CH.sub.3                                                                          H                                          229                                                                              CHF.sub.2     O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3  194-195                          230                                                                              CHF.sub.2     S CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   231                                                                              CF.sub.2CHF.sub.2                                                                           O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   232                                                                              C.sub.2 F.sub.5                                                                             O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   233                                                                              CF.sub.3      O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   234                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   235                                                                              (CH.sub.2).sub.2OC.sub.2 H.sub.5                                                            O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub. 3                                  236                                                                              CH.sub.2CH.sub.2 Cl                                                                         O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   237                                                                              CClCHCl       O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   238                                                                              CH.sub.2CHCH.sub.2                                                                          O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   239                                                                              CH.sub.2CCH   O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   240                                                                              CH.sub.2OCH.sub.3                                                                           O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   241                                                                              (CH.sub.2).sub.2SCH.sub.3                                                                   O CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   242                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   S CH OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   243                                                                              CHF.sub.2     O CH SCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   244                                                                              CHF.sub.2     O CH OCH.sub.2                                                                              CH.sub.3                                                                          H                                          245                                                                              CF.sub.3      O CH OCHF.sub.2                                                                             CH.sub.3                                                                          H                                          246                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCHF.sub.2                                                                             CH.sub.3                                                                          H                                          247                                                                              (CH.sub.2)CCH O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  197-199                          248                                                                              CH.sub.2CHCHCH.sub.3                                                                        O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  182-184                          249                                                                              CH.sub.2CHCH.sub.2                                                                          O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  177-180                          250                                                                              CHF.sub.2     O N  Cl       CH.sub.3                                                                          CH.sub.3  199-200                          251                                                                              (CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  173-174                          252                                                                              CH.sub.2CH.sub.2 Cl                                                                         O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  181-182                          253                                                                              CF.sub.2CHF.sub.2                                                                           O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3  169-170                          254                                                                              CHF.sub.2     O N  OCH.sub.3                                                                              CH.sub.3                                                                          CH.sub.2 CH.sub.3                                                                       172-173                          255                                                                              CH.sub.2CCH   O N  OCH.sub.2CF.sub.3                                                                      CH.sub.3                                                                          CH.sub.3  160-164                          256                                                                              CHF.sub.2     S N  OCH.sub.3                                                                              CH.sub.3                                                                          H         197-198                          257                                                                              CHF.sub.2     O N  OCHF.sub.2                                                                             CH.sub.3                                                                          CH.sub.3                                   __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR13##                                                                                                                  m.p.                            No.  A             X     E    R.sub.3                                                                             R.sub.4                                                                            R.sub.5                                                                            °C.                      ______________________________________                                        301  CHF.sub.2     O     CH   OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           195-                                                                          196                             302  CHF.sub.2     O     CH   OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            303  CHF.sub.2     O     N    OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                             304  CHF.sub.2     O     N    OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            305  CHF.sub.2     S     N    OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            306  CHF.sub.2     S     N    OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                             307  CHF.sub.2     S     CH   OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            308  CHF.sub.2     S     CH   OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                             309  CH.sub.2CHCH.sub.2                                                                          O     CH   OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                             310  CH.sub.2CHCH.sub.2                                                                          O     CH   OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            311  CH.sub.2CHCH.sub.2                                                                          O     N    OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                             312  CH.sub.2CHCH.sub.2                                                                          O     N    OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            313  (CH.sub.2).sub.2OCH.sub.3                                                                   O     CH   OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            314  (CH.sub.2).sub.2OCH.sub.3                                                                   O     CH   OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                             315  (CH.sub.2).sub.2OCH.sub.3                                                                   O     N    OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                            316  (CH.sub.2).sub.2OCH.sub.3                                                                   O     N    OCH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                             ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________     ##STR14##                                                                    No.                                                                              A           E  X R.sub.2                                                                             R.sub.3                                                                           R.sub.4                                                                          R.sub.5                                                                           m.p. °C.                          __________________________________________________________________________    401                                                                              CHF.sub.2   CH O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     402                                                                              CHF.sub.2   CH O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    403                                                                              CHF.sub.2   N  O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          169-172                                  404                                                                              CHF.sub.2   N  O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    405                                                                              CHF.sub.2   CH O 5-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          210-211                                  406                                                                              CHF.sub.2   CH O 5-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    407                                                                              CHF.sub.2   N  O 5-Cl  OCH.sub. 3                                                                        CH.sub.3                                                                         CH.sub.3                                                                          171-172                                  408                                                                              CHF.sub.2   N  O 5-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    409                                                                              CHF.sub.2   CH O 6-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     410                                                                              CHF.sub.2   CH O 6-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    411                                                                              CHF.sub.2   N  O 6-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          149-151                                  412                                                                              CHF.sub.2   N  O 6-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    413                                                                              CHF.sub.2   CH O 5-CHF.sub.2                                                                         OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     414                                                                              CHF.sub.2   CH O 5-CHF.sub.2                                                                         OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    415                                                                              CHF.sub.2   N  O 5-CHF.sub.2                                                                         OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     416                                                                              CHF.sub.2   N  O 5-CHF.sub.2                                                                         OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    417                                                                              CHF.sub.2   CH O 5-COOCH.sub.3                                                                       OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     418                                                                              CHF.sub.2   CH O 5-COOCH.sub.3                                                                       OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    419                                                                              CHF.sub.2   N  O 5-COOCH.sub.3                                                                       OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     420                                                                              CHF.sub.2   N  O 5-COOCH.sub.3                                                                       OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    421                                                                              CHF.sub.2   CH O 6-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     422                                                                              CHF.sub.2   CH O 6-F   OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    423                                                                              CHF.sub.2   N  O 6-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                     424                                                                              CHF.sub.2   N  O 6-F   OCH.sub.3                                                                         CH.sub.3                                                                         OCH.sub.3                                    425                                                                              CH.sub.2CCH N  O 5-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          194 (decomp.)                            426                                                                              CH.sub.2CHCH.sub.2                                                                        N  O 5-CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          194-196                                  427                                                                              CH.sub.2CHCH.sub.2                                                                        N  O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          192-193                                  428                                                                              CH.sub.2CCH N  O 5-CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          208-212                                  429                                                                              CH.sub.2CHCH.sub.2                                                                        N  O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          192-193                                  430                                                                              CH.sub.2CCH N  O 5-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          194-198 (decomp.)                        431                                                                              CH.sub.2CCH N  O 5-CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          208-212                                  432                                                                              CH.sub.2CCH N  O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          186-189                                  433                                                                              CH.sub.2C(CH.sub.3)CH.sub.2                                                               N  O 5-F   OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          187-188                                  434                                                                              CH.sub.2CHCH.sub.2                                                                        N  O 5-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          174-176                                  435                                                                              CH.sub.2C(CH.sub.3)CH.sub.2                                                               N  O 5-Cl  OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          153-155 (decomp.)                        436                                                                              CH.sub.2CHCH.sub.2                                                                        N  O 5-CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          194-196                                  __________________________________________________________________________

FORMULATION EXAMPLES EXAMPLE 3 Formulation Examples for activeingredients of the formula I (%=percent by weight)

    ______________________________________                                        (a) Wettable powder (a)     (b)     (c)                                       ______________________________________                                        active ingredient   20%     60%     0.5%                                      sodium lignin sulfonate                                                                           5%      5%      5%                                        sodium lauryl sulfate                                                                             3%      --      --                                        sodium diisobutylnaphthalene                                                                      --      6%      6%                                        sulfonate                                                                     octylphenolpolyethylene glycol                                                                    --      2%      2%                                        ether (7-8 mols of ethylene oxide)                                            highly dispersed silicic acid                                                                     5%      27%     27%                                       kaolin              67%     --      --                                        sodium chloride     --      --      59.5%                                     ______________________________________                                    

The active ingredient is well mixed with the additives and ground in asuitable mill. There are obtained wettable powders which can be dilutedwith water to give suspensions of the concentration desired.

    ______________________________________                                        (b) Emulsion concentrate                                                                             (a)    (b)                                             ______________________________________                                        active ingredient      10%    1%                                              octylphenolpolyethylene glycol ether                                                                  3%    3%                                              (4-5 mols of ethylene oxide)                                                  calcium dodecyl benzene sulfonate                                                                     3%    3%                                              castor oil polyglycol ether                                                                           4%    4%                                              (36 mols of ethylene oxide)                                                   cyclohexanone          30%    10%                                             xylene mixture         50%    79%                                             ______________________________________                                    

Emulsions of the concentration desired can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dust          (a)     (b)                                                 ______________________________________                                        active ingredient 0.1%     1%                                                 talcum            99.9%   --                                                  kaolin            --      99%                                                 ______________________________________                                    

Dusts ready for use are obtained by mixing the active-ingredient withthe carriers, and grinding the mixture in a suitable mill.

    ______________________________________                                        (d) Extruder granulate                                                                            (a)    (b)                                                ______________________________________                                        active ingredient   10%    1%                                                 sodium lignin sulfonate                                                                            2%    2%                                                 carboxymethylcellulose                                                                             1%    1%                                                 kaolin              87%    96%                                                ______________________________________                                    

The active ingredient is mixed with the additives, and the mixture isthen ground and moistened with water. It is extruded and subsequentlydried in a stream of air.

    ______________________________________                                        (e) Coated granulate                                                          ______________________________________                                        active ingredient    3%                                                       polyethylene glycol (MG 200)                                                                       3%                                                       kaolin               94%                                                      ______________________________________                                    

The finely ground active ingredient is uniformuly applied, in a mixer,to the kaolin moistened with polyethylene glycol. Non-dusty coatedgranules are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrate                                                                          (a)    (b)                                              ______________________________________                                        active ingredient     40%    5%                                               ethylene glycol       10%    10%                                              nonylphenolpolyethylene glycol                                                                       6%    1%                                               ether (15 mols of ethylene oxide)                                             sodium lignin sulfonate                                                                             10%    5%                                               carboxymethylcellulose                                                                               1%    1%                                               37% aqueous formaldehyde solution                                                                   0.2%   0.2%                                             silicone oil in the form of a                                                                       0.8%   0.8%                                             75% aqueous emulsion                                                          water                 32%    77%                                              ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. There is thus obtained a suspension concentrate from whichcan be produced, by dilution with water, suspensions of theconcentration desired.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        active ingredient      5%                                                     isopropylamine         1%                                                     octylphenolpolyethylene glycol ether                                                                 3%                                                     (78 mols of ethylene oxide)                                                   water                  91%                                                    ______________________________________                                    

BIOLOGICAL EXAMPLES EXAMPLE 4 Herbicidal action before emergence of theplants

Plastics pots are filled with expanded vermiculite (density: 0.135g/cm³, water-absorption capacity: 0.565 l/l). After saturation of thenon-adsorptive vermiculite with an aqueous active-substance emulsion indeionised water, which contains the active ingredient at a concentrationof 70.8 ppm, seeds of the following plants are sown on the surface:Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitariasanguinalis. The test vessels are subsequently kept in a climaticchamber at 20° C., with an illumination of about 20 k lux and a relativehumidity of 70%. During the germination phase of 4 to 5 days, the potsare covered over with light-permeable material in order to raise thelocal air humidity and watered with deionised water. After the 5th day,0.5% of a commercial liquid fertiliser (®Greenzit) is added to thewater. The test is evaluated 12 days after sowing, and the effect on thetest plants assessed according to the following scale of ratings:

1 plants have not germinated or are totally destroyed

2-3 very strong action

4-6 medium action

7-8 weak action

9 no action (as untreated control plants)

Pre-emergence action

Concentration of the active-ingredient emulsion: 70.8 ppm

    ______________________________________                                        Active    Test plant                                                          ingredient No                                                                           Nasturtium                                                                              Stellaria agroutis                                                                             Digitaria                                ______________________________________                                         1        2         --        --     --                                        6        2         2         1      --                                        13       3         3         1      2                                         17       2         --        --     --                                        20       1         1         1      --                                        22       3         --        --     --                                        30       1         2         1      1                                         55       1         3         1      1                                        106       1         3         1      2                                        157       1         2         1      2                                        158       2         3         1      3                                        160       2         2         1      --                                       162       3         --        --     --                                       172       1         1         1      --                                       174       2         5         1      --                                       176       2         2         1      --                                       179       2         --        --     --                                       182       6         --        --     --                                       184       2         --        --     --                                       185       5         --        --     --                                       186       2         --        --     --                                       187       3         --        --     --                                       188       2         --        --     --                                       189       2         --        --     --                                       191       1         1         1      1                                        201       1         2         1      1                                        247       1         1         1      --                                       248       1         2         1      --                                       249       1         2         1      2                                        252       1         1         1      1                                        253       1         1         1      2                                        254       2         --        --     --                                       256       2         2         2      2                                        257       1         1         1      1                                        305       1         1         1      1                                        307       1         1         1      1                                        403       1         2         1      2                                        425       1         1         1      1                                        427       1         1         1      1                                        428       1         2         1      1                                        432       2         2         2      2                                        433       2         3         1      3                                        434       1         3         1      4                                        435       2         4         2      6                                        436       1         3         1      2                                        ______________________________________                                         --: not tested                                                           

EXAMPLE 5 Herbicidal action after emergence of the plants (contactaction)

A number of weeds and cultivated plants, both monocotyledonous anddicotyledonous, are sprayed after emergence, in the 4- to 6-leaf stage,with an aqueous active-ingredient dispersion in dosages of 4 kg ofactive ingredient per hectare, and then kept at 24° to 26° C. with45-60% relative humidity. The test results are evaluated 15 days afterthe treatment, and an assessment is made according to the same scale ofratings as in the pre-emergence test.

Post-emergence action

Applied amount: 4 kg of active ingredient per hectare

    ______________________________________                                        Comp.                       Sol-        Stel-                                                                              Phas-                            No.   Avena   Setaria Lolium                                                                              anum  Sinapis                                                                             laria                                                                              eolus                            ______________________________________                                        179   6       5       4     2     2     3    3                                182   9       9       5     2     2     3    3                                189   2       3       2     2     2     2    3                                ______________________________________                                    

EXAMPLE 6 Reduction in growth of tropical leguminous cover crops

The test plants (Centrosema plumieri and Centrosema pubescens) arecultivated to the fully grown stage, and then cut back to a height of 60cm. After 7 days, the the active ingredient is sprayed on in the form ofan aqueous emulsion. The test plants are maintained at 70% relativehumidity and with 6000 lux of artificial light, 14 hours per day, attemperatures of 27° C. by day and 21° C. by night. The test results areassessed 4 weeks after application of the emulsion. The new growthoccurring compared with that on the control plants is estimated andweighed, and the phytotoxicity is evaluated. The plants treated with theactive ingredients of the formula I show in this test a clear reductionin new growth (less than 20% of the new growth occurring on untreatedcontrol plants), without the test plants having suffered damage.

EXAMPLE 7 Regulation of growth of soya-bean plants

Soya-beans of the "Hark" variety are sown in plastic containers holdinga soil/peat/sand mixture in the ratio of 6:3:1, and are placed into aclimatic chamber. By optimum choice of temperature, illumination,fertiliser addition and watering, the plants develop over about 5 weeksinto the 5-6 trifoliate stage. At this point, the plants are sprayeduntil thoroughly dripping wet with the aqueous liquor of an activeingredient of the formula I, the active-ingredient concentration beingup to 100 g of active ingredient per hectare. An assessment of theresults is made about 5 weeks after application of the activeingredient. The active ingredients of the formula I produce a markedincrease in the number and in the weight of the pods on the leadingshoots compared with the number and weight of pods on the untreatedcontrol plants.

EXAMPLE 8 Reduction of growth of cereals

The cereal varieties Hordeum vulgare (spring barely) and Secale (springrye) are sown in plastics pots containing containing sterilised soil ina greenhouse, and watered as required. The young shoots are sprayed,about 21 days after sowing, with the aqueous spray liquor of an activeingredient of the formula I. The amount applied is up to 100 g of activeingredient per hectare, and 21 days after application, the growth of thecereals is assessed. The treated plants show a reduction in the extentof new growth compared with that on the untreated control plants (60-90%of the new growth on the control plants), and also in part an increasein the diameter of the stems of the plants.

EXAMPLE 9 Reduction of growth of grasses

The grasses Lolium perenne, Poa pratensis, Festuca ovina, Dactylisglomerata and Cynodon dactylon are sown, in a greenhouse, in plasticsdishes containing a soil/peat/sand mixture (6:3:1), and watered asrequired. The emerged grasses are cut back weekly to a height of 4 cm.and are sprayed, about 50 days after sowing and one day after the finalcutting, with the aqueous spray liquor of the active ingredient of theformula I. The amount of active ingredient corresponds, when converted,to up to 100 g per hectare. The growth of the grasses is assessed 21days after application.

The compounds of the formula I effect a reduction of new growth ofaround 10-30%, compared with the new growth of the untreated controlgrasses.

What is claimed is:
 1. A compound selected from the group consisting ofa pyrimidinylsulfonylurea of the formula: ##STR15## wherein Z is O orS;A is (i) alkynyl of 3 to 6 carbon atoms, (ii) an alkyl group of 1 to 6carbon atoms substituted with halo, alkoxy of 1 to 4 carbon atoms,alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms,alkylsulfonyl of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 carbon atoms,haloalkyl sulfinyl or haloalkylsulfonyl; or (iii) an alkenyl group of 2to 6 carbon atoms which is unsubstituted or substituted with halo,alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms,alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbonatoms, haloalkoxy of 1 to 4 carbon atoms, haloalkyl sulfinyl orhaloalkylsulfonyl; R₁ is hydrogen, halo, alkyl of 1 to 5 carbon atoms,alkenyl of 2 to 5 carbon atoms, or R₆ --Y-- in whichY is O, S, SO, orSO₂ and R₆ is alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbonatoms, or alkynyl of 2 to 6 carbon atoms; R₂ is hydrogen, halo, alkyl of1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, haloalkyl of 1 to 4carbon atoms, R₅ --Y--, nitro, R₇ OCO--, or R₈ R₉ NCO--, in whichY andR₆ are as defined above; R₇ is an alkyl of 1 to 5 carbon atoms, alkenylof 2 to 5 carbon atoms, or alkynyl of 2 to 6 carbon atoms; and each ofR₈ and R₉ is independently hydrogen, alkyl of 1 to 5 carbon atoms,alkenyl of 2 to 5 carbon atoms or alkynyl of 2 to 6 carbon atoms; R₃ ishydrogen, halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbonatoms, alkylthio of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbonatoms, haloalkoxy of 1 to 4 carbon atoms, or alkoxyalkyl of up to 4carbon atoms; R₄ is hydrogen, methyl, or ethyl; and R₅ is hydrogen,alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 3 carbon atoms,methoxymethyl, cyanomethyl, or cyanoethyl; and the salts thereof.
 2. Acompound according to claim 1 and selected from the group consisting ofa pyrimidinylsulfonylurea of the formula: ##STR16## wherein A isdifluoromethyl, trifluoromethyl, 1,1,2,2-tetrafluoroethyl,pentafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, or 2-chloroethyl;R₃ ischloro, methyl, ethyl, isopropyl, methoxy, ethoxy, isopropoxy,methylthio, difluoromethoxy, or 2,2,2-trifluoroethoxy; R₄ is hydrogen,methyl, or ethyl; and R₅ is hydrogen, methyl, ethyl, t-butyl, methoxy,cyanomethyl, or cyanoethyl; and the salts thereof.
 3. A compoundaccording to claim 1, wherein Z is oxygen.
 4. A compound according toclaim 3, wherein R₄ and R₅ together have at most 4 carbon atoms.
 5. Acompound according to claim 2 wherein A is haloalkyl of 1 to 4 carbonatoms.
 6. A compound according to claim 2, wherein A is C₃ -C₄ -alkynyl,C₂ -C₆ -alkenyl or C₂ -C₆ -haloalkenyl, or C₁ -C₃ -alkyl substituted byC₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulfinyl or C₁ -C₄-alkylsulfonyl.
 7. A compound according to claim 2, wherein R₁ ishydrogen, and R₂ is hydrogen, halogen, methyl or --COO--C₁ -C₃ -alkyl.8. A compound according to claim 7, wherein R₁ and R₂ are hydrogen.
 9. Acompound according to claim 8, wherein R₃ is methoxy, ethoxy,difluoromethoxy, 2,2,2-trifluoroethoxy, methyl, ethyl, fluoromethyl orchloromethyl, R₄ is hydrogen, methyl or ethyl, and R₅ is methyl orethyl. 10.N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-(4-dimethylamino-6-methoxypyrimidin-2-yl)-ureaaccording to claim
 1. 11.N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-(4-methylamino-6-methoxypyrimidin-2-yl)-ureaaccording to claim
 1. 12. A herbicidal and growth-regulating compositionwhich comprises an effective amount of at least one compound accordingto claim 1, together with a suitable carrier therefor.
 13. A method ofcontrolling undesired plant growth, which method comprises applyingthereto or to the locus thereof a herbicidally effective amount of acompound according to claim
 1. 14. A method of regulating plant growth,which method comprises applying thereto or to the locus thereof aneffective amount of a compound according to claim
 1. 15. A methodaccording to claim 13 for selectively controlling weeds in crops ofcultivated plants, which method comprises applying the compoundpre-emergence or post-emergence.
 16. A method according to claim 15 forcontrolling weeds in crops of sugar cane, cereals, rice and cotton. 17.A method according to claim 15 for controlling weeds in crops ofsoybeans.
 18. A method according to claim 14 for suppressing plantgrowth beyond the two-leaf stage, which method comprises applying thecompound pre-emergence.
 19. A method of regulating plant growth in orderto achieve greater yields, which method comprises applying thereto or tothe locus thereof an effective amount of a compound according toclaim
 1. 20. A method according to claim 19 for regulating plant growthin crops of soybeans.
 21. A method according to claim 14 for suppressingthe growth of cover crop Leguminosae.
 22. A compound selected from thegroup consisting of a pyrimidinylsulfonylurea of the formula: ##STR17##wherein Z is O or S;A is (i) alkynyl of 3 to 6 carbon atoms, or (ii) analkyl group of 1 to 6 carbon atoms substituted with halo, alkoxy of 1 to4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, haloalkoxy of 1 to4 carbon atoms, haloalkyl sulfinyl or haloalkylsulfonyl; R₁ is hydrogen,halo, alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, orR₆ --Y-- in whichY is O, S, SO, or SO₂ and R₆ is alkyl of 1 to 5 carbonatoms, alkenyl of 2 to 5 carbon atoms, or alkynyl of 2 to 6 carbonatoms; R₂ is hydrogen, halo, alkyl of 1 to 5 carbon atoms, alkenyl of 2to 5 carbon atoms, haloalkyl of 1 to 4 carbon atoms, R₅ --Y--, nitro, R₇OCO--, or R₈ R₉ NCO--, in whichY and R₆ are as defined above; R₇ is analkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, or alkynylof 2 to B 6 carbon atoms; and each of R₈ and R₉ is independentlyhydrogen, alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atomsor alkynyl of 2 to 6 carbon atoms; R₃ is hydrogen, halo, alkyl of 1 to 4carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbonatoms, haloalkyl of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 carbonatoms, or alkoxyalkyl of up to 4 carbon atoms; R₄ is hydrogen, methyl,or ethyl; and R₅ is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1to 3 carbon atoms, methoxymethyl, cyanomethyl, or cyanoethyl; and thesalts thereof.
 23. A compound according to claim 22 wherein A ishaloalkyl of 1 to 4 carbon atoms.
 24. A compound according to claim 22and selected from the group consisting of a pyrimidinylsulfonylurea ofthe formula: ##STR18## wherein A is difluoromethyl,1,1,2,2-tetrafluoroethyl, or 2-chloroethyl;R₃ is chloro, methyl, ethyl,isopropyl, methoxy, ethoxy, isopropoxy, methylthio, difluoromethoxy, or2,2,2-trifluoroethoxy; R₄ is hydrogen, methyl, or ethyl; and R₅ ishydrogen, methyl, ethyl, t-butyl, methoxy, cyanomethyl, or cyanoethyl;and the salts thereof.
 25. The compound according to claim 24 which isN-(2-difluoromethylthiophenylsulfonyl)-N'-(4-dimethylamino-6-methoxypyrimidin-2-yl)urea.